CN101786695B - Seawater ammonia removal device - Google Patents
Seawater ammonia removal device Download PDFInfo
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- CN101786695B CN101786695B CN2010101208259A CN201010120825A CN101786695B CN 101786695 B CN101786695 B CN 101786695B CN 2010101208259 A CN2010101208259 A CN 2010101208259A CN 201010120825 A CN201010120825 A CN 201010120825A CN 101786695 B CN101786695 B CN 101786695B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a seawater ammonia removal device relating to a water processing device. The seawater ammonia removal device is provided with a zeolite exchange processing tower, an attached fixed stand, a raw water storage tank, an effluent storage tank and a scouring pipe, wherein the bottom in the zeolite exchange processing tower is provided with a facing bar which is provided with a switching layer, and the switching layer is provided with a modified zeolite layer, a gravel and a cobble layer from top to bottom; and the bottom of the processing tower is provided with a drain pipe, and the top of the processing tower is provided with a seawater inlet, and a valve is connected with the processing tower by a metering pump and the scouring pipe; the attached fixed stand is provided with an upper layer fixed stand and a lower layer fixed stand, the effluent storage tank and the raw water storage tank are respectively arranged on the upper layer fixed stand and the lower layer fixed stand; the effluent storage tank is arranged above the raw water storage tank, and a level controller is respectively arranged in each of two water storage tanks; the top of the raw water storage tank is provided with a seawater inlet valve, and the bottom of the raw water storage tank is provided with a drain valve; and the bottom of the effluent storage tank is provided with an outlet valve, and the seawater outlet of the effluent storage tank is connected to the drain pipe on the bottom of the processing tower.
Description
Technical field
The present invention relates to a kind of water treatment device, especially relate to a kind for the treatment of unit for removing Ammonia In Sea Water.
Background technology
Along with developing rapidly of economy; the expansion of industry size and the aggravation of mankind's activity; the quantity discharged of sanitary sewage and trade effluent increases sharply; ammonia nitrogen is as one of important component of body eutrophication, become at present the wastewater treatment qualified discharge leading indicator ([1] " integrated wastewater discharge standard " GB 8978-1996. .1996 of State Environmental Protection Administration).
For aquaculture, in recent years, along with improving constantly of aquatic products intensive culture level, the rapid rising of pollutant load in the unit of water body, it is low to cause that therefrom dissolved oxygen appears in aquaculture water, and the problems such as a large amount of accumulation of the nuisances such as ammonia nitrogen cause the normal living environment of aquaculture organisms to wreck.Especially in prawn culturing, ammonia-nitrogen content has become the key of supporting the shrimp success.In 1989, China was issuing relevant emission standard ([2] " water quality standard for fishery " GB11607-1989. State Environmental Protection Administration 1989) aspect the ammonia control of aquiculture waste water.At present, the method for the control of the ammonia and nitrogen pollution in aquaculture has: (1) is changed in a large number the new water of notes and is diluted to reduce ammonia nitrogen concentration; (2) ammonia nitrogen in the employing aeration stripping water; (3) remove ammonia nitrogen and adopt photosynthetic bacterium to regulate with chlorine residue sterilization improve water quality etc. ([3] Zhang Renzhi, Chu Huaning, Han Enshan etc. the development of ammonia nitrogenous wastewater treatment technology [J]. Chinese environmental management cadre academy journal, 2005.9:91-94).These ways exist the high and chemical agent usage quantity problem of energy consumption, and unsatisfactory to the removal effect of ammonia nitrogen.
Natural zeolite is moisture frame shape basic metal or alkaline earth metal aluminosilicate mineral, generally can chemical formula AmXpOZp.nH
2O represents that X is Si in the formula, Al; A is Na., K......Its structure is by silicon-oxy tetrahedron (SiO
4) and aluminum-oxygen tetrahedron (AlO
4) unit interconnects by oxo bridge and form.This tridimensional network of zeolite is very loose, has many holes.Because the natural zeolite crystal forms a lot of cavitys and duct by silicon (aluminium) oxygen tetrahedron, wherein in occupation of positively charged ion and water molecules, when making their part or all of dehydrations through braising in soy sauce, its crystallization skeleton does not destroy, thereby form the one by one very large hole of internal surface, adsorbable and store a large amount of molecules.Because contacting of the positively charged ion in the crystallization of zeolites skeleton and skeleton is more weak, so when zeolite contacted with the aqueous solution of certain metal-salt, the metallic cation in the solution can enter in the zeolite, and the positively charged ion in the zeolite can exchanged get off to enter in the solution.Its exchange process can be expressed as follows: X
+Z
-+ NH
4 +→ NH
4 +Z
-+ X
+, Z
-The negatively charged ion screen work of expression aluminosilicate, X
+The expression exchange ion.It is large that zeolite has adsorptive capacity to the absorption of ammonia nitrogen, highly selective, the efficient adsorption characteristics ([4] Guo Shouguo, He Bin. Non-metallic Mineral Resource Exploitation utilization [M]. Wuhan: press of China University of Geosciences, 1992; [5] Zhang Xi, Wu Weizhong, Wen Donghui etc. absorption and the desorb [J] of ammonia nitrogen on natural zeolite. environmental chemistry, 2003,22 (2): 167-171; [6] Yuan Junsheng. zeolite process industrial sewage ammonia nitrogen Study on treatment technology [J]. Techniques and Equipment for Environmental Pollution Control, 2002,12 (3): 60-63; [7] Li Jian, Yuan Youxian. natural zeolite is used for aquaculture research [J]. marine fishery research, 1987,8:55-60).
In the ion-exchange performance research report of natural zeolite, find, natural and through the zeolite of physico-chemical processes modification to ammonia nitrogen demonstrate good ion exchangeable and reproducibility ([8] Kithome M.Kinethics of ammonium adsorption anddesorption by natural zeolite clinoptilolite[J] .Soil Sci.Soc Am J, 1998,62 (3): 622-629; [9] Yang Shengke, Wang Wenke, Li Xiang etc. zeolite is removed analysis of Influential Factors and the mechanism of action of ammonia nitrogen in the underground water and is inquired into [J]. Xi'an engineering college journal, 2000,22 (3): 69-72; [10] Li Ye etc. zeolite is removed the experimental study [J] of low-concentration ammonia-nitrogen in the water source. Wuhan University of Technology's journal, 2003,2:25-28; [11] Jorgensen T C, Weatherley L R.Ammonia removal from wastewaterby ion exchange in the presence of organic contaminants[J] .Wat.Res., 2003,37:1723-1728; [12] Kataoka, Katsushi.Method for removal of ammonium nitrogen from organic wastewater bybiological nitration and denitrification with zeolite regeneration.Japan, CLASS:ICM:C02F003-34.Jpn, Kokai Tokkyo Koho JP 09314186 A29 Dec 1997), the natural zeolite by modification particularly, better ([13] Wang Dehua of removal effect to ammonia nitrogen, Fei Weiyang. the ammonium ion exchange balance [J] of sodium remodeling using natural clinoptilolite. ion-exchange and absorption, 2002,18 (4): 343-348; [14] Zhao Dan, Wang Shuguang etc. the research of Ammionia Removal From Water Using Remodeled Clinoptilolite [J]. environmental chemistry 2001,1 (22): 12-16).Nearest result of study shows that when seawater was carried out ion exchange treatment, the modified natural zeolite can make the ammonia nitrogen in the seawater obtain removing.The mariculture technique that seawater quality is had relatively high expectations, use zeolite seawater cleaning treatment unit very necessary ([15] Gao Hongmei. zeolite is removed the effect research [J] of ammonia nitrogen in the aquaculture water. Hua Zhong Agriculture University's journal, 2005.1:9-11; [16] Xiong Xiaojing, Ye Junlei, Wang Xinhong etc. the experimental study of Treatment of Low Concentration Ammonia Wastewater by Natural Zeolite [J]. Xiamen University's journal (natural science edition), 2006,45 (6): 828-831; [17] Liu Yuanjin, Zhang Xinming etc. natural zeolite is removed effect [J] to the nitrogen phosphorus of fish pond water and sanitary sewage. agriculture environmental protection, 2002,4:331-333).
Summary of the invention
The object of the present invention is to provide a kind of seawater ammonia removal device.
The present invention is provided with zeolite exchange treating column, attached fixed stand, former water water tank, water outlet water tank and acid pickling tube.
Bottom in the zeolite exchange treating column is provided with back up pad, be provided with the exchange layer in back up pad, the exchange layer is provided with modified zeolite layer, grit layer and pebbles layer from top to bottom successively, back up pad is provided with permeable hole, permeable hole is provided with the filter filter cap, is provided with water shoot in zeolite exchange treating column bottom, is used for discharging the backwashing water that contains suspended substance and deposition solid, the top of zeolite exchange treating column is provided with the seawater water-in, and valve is connected with acid pickling tube through volume pump with the zeolite exchange treating column.
Attached fixed stand is established upper strata fixed stand and lower floor's fixed stand, the water outlet water tank is located on the fixed stand of upper strata, former water water tank is located on lower floor's fixed stand, the water outlet water tank is positioned at former water water tank top, be equipped with fluid level controller in former water water tank and the water outlet water tank, the top of former water water tank is provided with the seawater water intaking valve, the bottom of former water water tank is provided with water discharge valve, the bottom of water outlet water tank is provided with outlet valve, and the seawater water outlet of water outlet water tank is arranged in the water shoot of zeolite exchange treating column bottom through valve.
Described modified zeolite layer can adopt using natural clinoptilolite, particle diameter is 0.5～1.5mm, the height of modified zeolite layer can be 50～90cm, the grit diameter of described grit layer can be 2～5mm, the height of grit layer can be 10～30cm, the cobble diameter of described pebbles layer can be 1～3cm, and the height of pebbles layer can be 10～30cm.
The Inlet and outlet water of zeolite exchange treating column, former water water tank and water outlet water tank is controlled by water pump; Acid pickling tube is connected with volume pump, and the required hydrochloric acid soln of pickling is controlled by volume pump.
The present invention adopts the modified natural zeolite as the exchange treatment media that removes Ammonia In Sea Water, utilize the zeolite ion selectivity good to ammonia nitrogen, with hydrochloric acid soln as regenerator, the zeolite exchange treating column is core apparatus of the present invention, it possesses exchange and processes, exchanges the operating functions such as layer back flushing and zeolite regeneration, the purpose that removes Ammonia In Sea Water can be reached, the requirement of mariculture water can be satisfied.
Description of drawings
Fig. 1 is that the structure of the embodiment of the invention forms schematic diagram.
Fig. 2 is the structural representation of the zeolite exchange treating column of the embodiment of the invention.
Fig. 3 is the structural representation of the interior back up pad of the zeolite exchange treating column of the embodiment of the invention.
Fig. 4 is the former water water tank of the embodiment of the invention and the structural representation of water outlet water tank.
Fig. 5 is that the zeolite consumption of the embodiment of the invention is on the figure that affects of ammonia nitrogen removal effect.In Fig. 5, X-coordinate is zeolite consumption (g), and ordinate zou is water outlet ammonia nitrogen concentration (mg/L).
Fig. 6 is the ammonia nitrogen concentration of the embodiment of the invention and the graph of a relation of ammonia nitrogen removal effect.In Fig. 6, X-coordinate is initial ammonia nitrogen concentration (mg/L), ordinate zou clearance (%).
Fig. 7 is that the pH value of the embodiment of the invention is on the figure that affects of ammonia nitrogen removal effect.In Fig. 7, X-coordinate is the pH value, and ordinate zou is water outlet ammonia nitrogen concentration (mg/L).
Fig. 8 is that the concentration of hydrochloric acid of the embodiment of the invention is on the figure that affects of ammonia nitrogen elute effect.In Fig. 8, X-coordinate is concentration of hydrochloric acid (mol/L), and ordinate zou is eluting rate (%).
Fig. 9 is the treatment effect figure of ammonia nitrogen in the continuous operational process of the embodiment of the invention.In Fig. 9, X-coordinate is fate, and ordinate zou is water outlet ammonia nitrogen concentration (mg/L).
Embodiment
Referring to Fig. 1～4, the embodiment of the invention is provided with zeolite exchange treating column 1, attached fixed stand 18, former water water tank 14, water outlet water tank 17 and acid pickling tube 20.
Bottom in the zeolite exchange treating column 1 is provided with back up pad 22, be provided with the exchange layer in back up pad 22, the exchange layer is provided with modified zeolite layer 2, grit layer 3 and pebbles layer 4 from top to bottom successively, back up pad 22 is provided with permeable hole 221, permeable hole 221 is provided with the filter filter cap, be provided with water shoot 6 in zeolite exchange treating column 1 bottom, be used for discharging the backwashing water that contains suspended substance and deposition solid, the top of zeolite exchange treating column 1 is provided with the seawater water-in, and valve is connected with acid pickling tube 20 through volume pump 21 with zeolite exchange treating column 1.
Attached fixed stand 18 is established upper strata fixed stand and lower floor's fixed stand, water outlet water tank 17 is located on the fixed stand of upper strata, former water water tank 14 is located on lower floor's fixed stand, water outlet water tank 17 is positioned at former water water tank 14 tops, be equipped with fluid level controller 19 in former water water tank 14 and the water outlet water tank 17, the top of former water water tank 14 is provided with seawater water intaking valve 15, the bottom of former water water tank 14 is provided with water discharge valve 13, the bottom of water outlet water tank 17 is provided with outlet valve 16, and the seawater water outlet of water outlet water tank 17 is arranged in the water shoot 6 of zeolite exchange treating column 1 bottom through valve 10.
Described modified zeolite layer 2 can adopt using natural clinoptilolite, particle diameter is 0.5～1.5mm, the height of modified zeolite layer 2 can be 50～90cm, the grit diameter of described grit layer 3 can be 2～5mm, the height of grit layer 3 can be 10～30cm, the cobble diameter of described pebbles layer 4 can be 1～3cm, and the height of pebbles layer 4 can be 10～30cm.
The Inlet and outlet water of zeolite exchange treating column 1, former water water tank 14 and water outlet water tank 17 is by water pump 11 controls; Acid pickling tube 20 is connected with volume pump 21, and the required hydrochloric acid soln of pickling is by volume pump 21 controls.
The height of zeolite exchange treating column 1 of the present invention is 300cm, and diameter is 120cm, the high 50cm of base; Upper and lower sealing diameter is respectively 54cm and 28cm.It is carbon steel or plastics (annotate: the carbon steel tower body must carry out with epoxy coating the rotproofing of inwall before using) that tower body is made material.Zeolite exchange treating column 1 inner filtering layer cobble layer 4 (the cobble diameter be 1～3cm) with grit layer 3 (the grit diameter is that 2～5mm) floor height is 20cm, (zeolite type is using natural clinoptilolite to modified zeolite layer 2, and the particle diameter specification is 0.5～1.5mm) floor height 70cm.The diameter of back up pad 22 is 120cm, and the plate face is offered the permeable hole 221 that several apertures are 3cm, and pitch of holes is 10cm, is equipped with a plastic filter head filter cap (referring to Fig. 2) on each aperture.Attached fixed stand 18 has two-layer, and upper strata fixed stand and lower floor fixed stand are placed respectively the identical former water water tank 14 of volume and water outlet water tank 17 (tank mouth diameter is 50cm for high 92cm, diameter 85cm, and useful volume is 3m
3Referring to Fig. 3).
Fig. 5 has provided the present invention's modified zeolite dosage when to process ammonia nitrogen concentration be the 200mL seawater of 20mg/L and has been respectively 0,1, and 2,3,4 and the ammonia nitrogen removal characteristic of modified zeolite during 5g.Can find out, when the zeolite dosage is 2g, reach best ammonia nitrogen removal effect.As shown in Figure 6, along with the increase of ammonia nitrogen initial concentration, the deamination rate of zeolite also rises thereupon, and the deamination rate of zeolite reaches 28.2% of maximum when the ammonia nitrogen initial concentration is 20mg/L.Ammonia nitrogen concentration makes ammonium radical ion concentration be in higher level in the raising water, is conducive to zeolite exchange ammonium radical ion; But when the ammonia nitrogen initial concentration is higher than certain value, because zeolite exists saturated exchange capacity, continues to increase ammonia nitrogen concentration this moment clearance is reduced.
As shown in Figure 7, the deamination rate of zeolite is maximum when pH is 6 left and right sides.NH
4 +Dissociation equilibrium formula in water can be expressed as NH
4 +-NH
3+ H
+, along with the pH value reduces H
+The increase of concentration, balance shows as NH to moving to left
4 +Concentration increases.Because the polar group of zeolite surface is to NH
4 +Compare NH
3Larger avidity is arranged, can adsorb more NH
4 +But when the pH value is too low H can appear
+With NH
4 +Competition makes zeolite descend to the switching performance of ammonia nitrogen.Fig. 8 has provided at the wash-out regeneration effect of different concns hydrochloric acid to saturated zeolite.Can find out that concentration of hydrochloric acid is higher, the wash-out regeneration effect is better and variation tendency is obvious.But when concentration of hydrochloric acid surpassed 0.12mol/L continuation increase, regeneration effect changed not obvious.Consider the cost of regenerator hydrochloric acid and to the corrosive nature of equipment, select the 0.12mol/L concentration of hydrochloric acid for comparatively reasonable.The treatment effect of ammonia nitrogen as shown in Figure 9 in the continuous operational process, can find out, the device that loads fresh zeolite exchanges processing and has arrived saturated when running to the 3rd day, soak regeneration (first back flushing 1h with hydrochloric seawater to the zeolite in the exchange layer this moment, pass into again regenerated liquid, soak 24h), its regeneration rate can reach more than 90%.Enter the second exchange of taking turns after regenerative operation is finished and process operation, the exchange processing arrives saturated again when running to the 2.5th day, carry out again the second manipulation of regeneration of taking turns this moment, operation is processed in the exchange that enters third round after regenerative operation is finished, exchange is processed and again to be arrived when saturated, carries out the manipulation of regeneration of third round again.Zeolite is through manipulation of regeneration repeatedly, and it reduces gradually, and when regeneration rate is lower than 50%, the zeolite that must more renew arrives stable with assurance device to the treatment effect of ammonia nitrogen.
When exchanging the processing operation, valve 8 and valve 10 are opened, other all valve is all closed, start water pump 11 and the seawater in the former water water tank 14 is sent into the top of zeolite exchange treating column 1, successively by modified zeolite layer 2, grit layer 3 and pebbles layer 4, ammonia nitrogen in the seawater is exchanged processing, flow through uniformly afterwards back up pad 22 and (the filter filter cap that array is used for water distribution is housed on the plate, referring to Fig. 3), rely on kinetic pressure and the interior liquid level static pressure of exchange column of water pump 11, process water and send into water outlet water tank 17 via the pipeline of valve 10 controls.Water outlet water tank 17 and former water water tank 14 are interior all to be left overflow and fluid level controller 19 has been installed, when the liquid level that is lower than minimum liquid level or water outlet water tank when the liquid level of former water water tank is higher than the highest liquid level, start or switch off the pump 11, to avoid water pump to damage water pump because of dry running or the water outlet water tank runs off because of the water-filling overfill.The top and bottom of former water water tank is arranged with seawater water intaking valve 15 and water discharge valve 13, and the switching of water intaking valve 15 is discharged residuary water by the control of liquid level float control when water discharge valve 13 is used for cleaning water tank.The bottom of water outlet water tank is provided with outlet valve 16, opens when needing water, and the seawater of processing is delivered to cultivating workshop.
When carrying out backwash operation, valve 7 and valve 10 are opened, other all valve is all closed, switch on the pump 11, the pipeline that the seawater of former water water tank 17 is opened through valve 10 is sent into from zeolite exchange treating column bottom, direction flows through uniformly back up pad 22 and (the filter filter cap that array is used for water distribution is housed on the plate from bottom to top, referring to Fig. 3), flow through successively pebbles layer 4, grit layer 3 and modified zeolite layer 2, the suspended substance that is retained down in each filling bed is washed, and wash-down water flows out in top of tower, and the pipeline of opening through valve 7 enters water shoot 6 and puts into lower ditch.
When carrying out regenerative operation, at first will open valve 5 and emptying valve 12, other all valve is all closed, and the residual seawater in the tower is arranged ditches because of action of gravity through the water shoot 6 of exchange column bottom at this moment; When the water in confirming tower is discharged from fully, valve-off 5, emptying valve 12 continues to open, open valve 10, seawater in the water outlet water tank because of with tower in the syphonic effect that produces of liquid level difference of existence, through the pipeline that valve 10 is opened, at the bottom of tower, send in the tower, start simultaneously volume pump 21 concentrated hydrochloric acid solution in the pickling tank 20 is sent into same pipeline and processed sea water mixing and enter in the tower.Utilize hydrochloric acid to soak regeneration to exchanging saturated zeolite, soak time is 24h.When regenerative operation was finished, first valve-off 10 was opened valve 5 again, through water shoot 6 the regeneration liquid in the tower was put into lower ditch.
Claims (3)
1. a seawater ammonia removal device is characterized in that being provided with zeolite exchange treating column, attached fixed stand, former water water tank, water outlet water tank and acid pickling tube;
Bottom in the zeolite exchange treating column is provided with back up pad, be provided with the exchange layer in back up pad, the exchange layer is provided with modified zeolite layer, grit layer and pebbles layer from top to bottom successively, back up pad is provided with permeable hole, permeable hole is provided with the filter filter cap, be provided with water shoot in zeolite exchange treating column bottom, be used for discharging the backwashing water that contains suspended substance and deposition solid, the top of zeolite exchange treating column is provided with the seawater water-in, and the seawer outlet of zeolite exchange treating column bottom is connected with acid pickling tube with volume pump through valve successively;
Attached fixed stand is established upper strata fixed stand and lower floor's fixed stand, the water outlet water tank is located on the fixed stand of upper strata, former water water tank is located on lower floor's fixed stand, the water outlet water tank is positioned at former water water tank top, be equipped with fluid level controller in former water water tank and the water outlet water tank, the top of former water water tank is provided with the seawater water intaking valve, the bottom of former water water tank is provided with water discharge valve, the bottom of water outlet water tank is provided with outlet valve, and the seawater water outlet of water outlet water tank is arranged in the water shoot of zeolite exchange treating column bottom through valve;
Described modified zeolite layer adopts using natural clinoptilolite, and particle diameter is 0.5～1.5mm, and the height of modified zeolite layer is 50～90cm;
The grit diameter of described grit layer is 2～5mm, and the height of grit layer is 10～30cm;
The cobble diameter of described pebbles layer is 1～3cm, and the height of pebbles layer is 10～30cm.
2. a kind of seawater ammonia removal device as claimed in claim 1 is characterized in that the Inlet and outlet water of zeolite exchange treating column, former water water tank and water outlet water tank is controlled by water pump.
3. a kind of seawater ammonia removal device as claimed in claim 1 is characterized in that acid pickling tube is connected with volume pump, and the required hydrochloric acid soln of pickling is controlled by volume pump.
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|---|---|---|---|
| CN2010101208259A CN101786695B (en) | 2010-03-05 | 2010-03-05 | Seawater ammonia removal device |
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|---|---|---|---|
| CN2010101208259A CN101786695B (en) | 2010-03-05 | 2010-03-05 | Seawater ammonia removal device |
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| CN101786695A CN101786695A (en) | 2010-07-28 |
| CN101786695B true CN101786695B (en) | 2013-03-27 |
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